Insights into arsenic retention dynamics of Pleistocene aquifer sediments by in situ sorption experiments.

The migration of arsenic (As) enriched groundwater into Pleistocene aquifers as a consequence of extensive groundwater abstraction represents an increasing threat to the precious water resources in Asian delta regions. Pleistocene aquifer sediments are typically rich in FeIII-(hydr)oxides and are capable to adsorb high amounts of As. This results in a pronounced accumulation of As in Pleistocene aquifers, where high As groundwater infiltrates from adjacent Holocene aquifers. However, As retention by Pleistocene aquifers over long-term time scales remains largely unknown. We studied As sorption in situ by placing natural Pleistocene sediments and pure mineral phases directly inside groundwater monitoring wells at a study site near Hanoi (Vietnam). This in situ exposure allows for constant flushing of the samples with unaltered groundwater and the establishment of undisturbed sorption equilibria similar to those in local aquifer sediments, which is not readily attainable in traditional laboratory sorption experiments. The groundwaters in our experimental wells were characterized by different As concentrations (0.01-6.63 µmol/L) and redox states, reaching from suboxic to anoxic conditions (Eh of +159 to -4 mV). Results show that adsorption is the dominant As retention mechanism, independent from the respective groundwater chemistry (i.e. concentrations of dissolved P, HCO3- and Si). Whilst most of the As sorbed within the first week, sorption further increased slowly but consistently by 6-189%, respectively, within six months. Hence, the As sorption behavior of Pleistocene aquifer sediments should be determined over longer periods to avoid an underestimation of the As sorption capacity. Accompanying desorption experiments revealed that about 51% of the sorbed As was remobilized within six months when exposed to low As groundwater. We therefore conclude that a considerable proportion of the As accumulated in the aquifer sediments is prone to remobilization once the As concentrations in migrating groundwater decline. Remobilization of As should be considered in local water management plans to avoid contamination of precious groundwater resources with this As legacy.

Arsenic, manganese and aluminum contamination in groundwater resources of Western Amazonia (Peru).

This paper presents a first integrated survey on the occurrence and distribution of geogenic contaminants in groundwater resources of Western Amazonia in Peru. An increasing number of groundwater wells have been constructed for drinking water purposes in the last decades; however, the chemical quality of the groundwater resources in the Amazon region is poorly studied. We collected groundwater from the regions of Iquitos and Pucallpa to analyze the hydrochemical characteristics, including trace elements. The source aquifer of each well was determined by interpretation of the available geological information, which identified four different aquifer types with distinct hydrochemical properties. The majority of the wells in two of the aquifer types tap groundwater enriched in aluminum, arsenic, or manganese at levels harmful to human health. Holocene alluvial aquifers along the main Amazon tributaries with anoxic, near pH-neutral groundwater contained high concentrations of arsenic (up to 700µg/L) and manganese (up to 4mg/L). Around Iquitos, the acidic groundwater (4.2≤pH≤5.5) from unconfined aquifers composed of pure sand had dissolved aluminum concentrations of up to 3.3mg/L. Groundwater from older or deeper aquifers generally was of good chemical quality. The high concentrations of toxic elements highlight the urgent need to assess the groundwater quality throughout Western Amazonia.

Retardation of arsenic transport through a Pleistocene aquifer.

Groundwater drawn daily from shallow alluvial sands by millions of wells over large areas of south and southeast Asia exposes an estimated population of over a hundred million people to toxic levels of arsenic. Holocene aquifers are the source of widespread arsenic poisoning across the region. In contrast, Pleistocene sands deposited in this region more than 12,000 years ago mostly do not host groundwater with high levels of arsenic. Pleistocene aquifers are increasingly used as a safe source of drinking water and it is therefore important to understand under what conditions low levels of arsenic can be maintained. Here we reconstruct the initial phase of contamination of a Pleistocene aquifer near Hanoi, Vietnam. We demonstrate that changes in groundwater flow conditions and the redox state of the aquifer sands induced by groundwater pumping caused the lateral intrusion of arsenic contamination more than 120 metres from a Holocene aquifer into a previously uncontaminated Pleistocene aquifer. We also find that arsenic adsorbs onto the aquifer sands and that there is a 16-20-fold retardation in the extent of the contamination relative to the reconstructed lateral movement of groundwater over the same period. Our findings suggest that arsenic contamination of Pleistocene aquifers in south and southeast Asia as a consequence of increasing levels of groundwater pumping may have been delayed by the retardation of arsenic transport.

Arsenic pollution of groundwater in Vietnam exacerbated by deep aquifer exploitation for more than a century.

Arsenic contamination of shallow groundwater is among the biggest health threats in the developing world. Targeting uncontaminated deep aquifers is a popular mitigation option although its long-term impact remains unknown. Here we present the alarming results of a large-scale groundwater survey covering the entire Red River Delta and a unique probability model based on three-dimensional Quaternary geology. Our unprecedented dataset reveals that ∼7 million delta inhabitants use groundwater contaminated with toxic elements, including manganese, selenium, and barium. Depth-resolved probabilities and arsenic concentrations indicate drawdown of arsenic-enriched waters from Holocene aquifers to naturally uncontaminated Pleistocene aquifers as a result of > 100 years of groundwater abstraction. Vertical arsenic migration induced by large-scale pumping from deep aquifers has been discussed to occur elsewhere, but has never been shown to occur at the scale seen here. The present situation in the Red River Delta is a warning for other As-affected regions where groundwater is extensively pumped from uncontaminated aquifers underlying high arsenic aquifers or zones.

Contamination of drinking water resources in the Mekong delta floodplains: arsenic and other trace metals pose serious health risks to population.

This study presents a transnational groundwater survey of the 62,000 km(2) Mekong delta floodplain (Southern Vietnam and bordering Cambodia) and assesses human health risks associated with elevated concentrations of dissolved toxic elements. The lower Mekong delta generally features saline groundwater. However, where groundwater salinity is <1 g L(-)(1) Total Dissolved Solids (TDS), the rural population started exploiting shallow groundwater as drinking water in replacement of microbially contaminated surface water. In groundwater used as drinking water, arsenic concentrations ranged from 0.1-1340 microg L(-)(1), with 37% of the studied wells exceeding the WHO guidelines of 10 microg L(-)(1) arsenic. In addition, 50% exceeded the manganese WHO guideline of 0.4 mg L(-)(1), with concentrations being particularly high in Vietnam (range 1.0-34 mg L(-)(1)). Other elements of (minor) concern are Ba, Cd, Ni, Se, Pb and U. Our measurements imply that groundwater contamination is of geogenic origin and caused by natural anoxic conditions in the aquifers. Chronic arsenic poisoning is the most serious health risk for the ~2 million people drinking this groundwater without treatment, followed by malfunction in children's development through excessive manganese uptake. Government agencies, water specialists and scientists must get aware of the serious situation. Mitigation measures are urgently needed to protect the unaware people from such health problems.

Arsenic and manganese contamination of drinking water resources in Cambodia: coincidence of risk areas with low relief topography.

Arsenic contamination of groundwater has been identified in Cambodia, where some 100,000 family-based wells are used for drinking water needs. We conducted a comprehensive groundwater survey in the Mekong River floodplain, comprising an area of 3700 km(2) (131 samples, 30 parameters). Seasonal fluctuations were also studied. Arsenic ranged from 1 to 1340 microg L(-1) (average 163 microg L(-1)), with 48% exceeding 10 microg L(-1). Elevated manganese levels (57% >0.4 mg L(-1)) are posing an additional health threat to the 1.2 million people living in this area. With 350 people km(-2) potentially exposed to chronic arsenic poisoning, the magnitude is similar to that of Bangladesh (200 km(-2)). Elevated arsenic levels are sharply restricted to the Bassac and Mekong River banks and the alluvium braided by these rivers (Kandal Province). Arsenic in this province averaged 233 microg L(-1) (median 100 microg L(-1)), while concentrations to the west and east of the rivers were <10 microg L(-1). Arsenic release from Holocene sediments between the rivers is most likely caused by reductive dissolution of metal oxides. Regions exhibiting low and elevated arsenic levels are co-incident with the present low relief topography featuring gently increasing elevation to the west and east of a shallow valley-understood as a relict of pre-Holocene topography. The full georeferenced database of groundwater analysis is provided as Supporting Information.

Magnitude of arsenic pollution in the Mekong and Red River Deltas--Cambodia and Vietnam.

Large alluvial deltas of the Mekong River in southern Vietnam and Cambodia and the Red River in northern Vietnam have groundwaters that are exploited for drinking water by private tube-wells, which are of increasing demand since the mid-1990s. This paper presents an overview of groundwater arsenic pollution in the Mekong delta: arsenic concentrations ranged from 1-1610 microg/L in Cambodia (average 217 microg/L) and 1-845 microg/L in southern Vietnam (average 39 microg/L), respectively. It also evaluates the situation in Red River delta where groundwater arsenic concentrations vary from 1-3050 microg/L (average 159 microg/L). In addition to rural areas, the drinking water supply of the city of Hanoi has elevated arsenic concentrations. The sediments of 12-40 m deep cores from the Red River delta contain arsenic levels of 2-33 microg/g (average 7 microg/g, dry weight) and show a remarkable correlation with sediment-bound iron. In all three areas, the groundwater arsenic pollution seem to be of natural origin and caused by reductive dissolution of arsenic-bearing iron phases buried in aquifers. The population at risk of chronic arsenic poisoning is estimated to be 10 million in the Red River delta and 0.5-1 million in the Mekong delta. A subset of hair samples collected in Vietnam and Cambodia from residents drinking groundwater with arsenic levels >50 microg/L have a significantly higher arsenic content than control groups (<50 microg/L). Few cases of arsenic related health problems are recognized in the study areas compared to Bangladesh and West Bengal. This difference probably relates to arsenic contaminated tube-well water only being used substantially over the past 7 to 10 years in Vietnam and Cambodia. Because symptoms of chronic arsenic poisoning usually take more than 10 years to develop, the number of future arsenic related ailments in Cambodia and Vietnam is likely to increase. Early mitigation measures should be a high priority.

Polar fuel constituents: compound identification and equilibrium partitioning between nonaqueous phase liquids and water.

Groundwater contamination by fuel constituents from nonaqueous phase liquids (NAPLs) on top of the groundwater table is a widespread problem. While leaching of classical fuel constituents such as benzene, toluene, ethylbenzene, and xylenes (BTEX) from NAPLs into groundwater has been studied extensively, little is known about the identity and partitioning of polar fuel components. Our work shows that gasoline commonly contains appreciable amounts of aniline, phenol, and their alkyl-substituted homologues as well as a suite of other polar compounds. To assess the potential for leaching of such compounds from NAPLs into groundwater we measured the equilibrium fuel/water partitioning coefficients, Kfw, of some representative constituents in batch systems. Kfw values for the investigated phenols, anilines, benzotriazoles, and S-heterocycles ranged from 0.2 to 1700. These values are up to 3 orders of magnitude lower than the Kfw of benzene. The NAPL--water partitioning of anilines and phenols strongly depends on the compounds' structure as well as on pH and the gasoline composition (e.g., MTBE content). Linear free energy relationships (LFERs) using Kow or Cwsat failed to predict measured Kfw values of polar solutes. In contrast, a polyparameter approach taking into account molecular interactions (van der Waals forces, hydrogen bonds) between solutes and major gasoline components allows precise a-priori predictions of Kfw values of both polar and BTEX fuel constituents without any fit parameters. Since most of the polar fuel constituents studied here are extracted from NAPLs by groundwater much more efficiently than BTEX, such compounds could form contaminant plumes threatening receiving wells before detectable concentrations of BTEX are present.